US20170165157A1

US20170165157A1 - Method of treating hair

Info

Publication number: US20170165157A1
Application number: US15/380,373
Authority: US
Inventors: Robert Wayne Glenn, Jr.; Dariush HOSSEINPOUR; Kevin Lee Doyle
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2015-12-15
Filing date: 2016-12-15
Publication date: 2017-06-15
Anticipated expiration: 2036-12-15
Also published as: US10124951B2

Abstract

A method of treating the hair including providing a concentrated hair care composition in a dispenser. The concentrated hair care composition includes one or more silicones, perfume, an emulsifier system, and from about 2% to about 10% high melting point fatty compounds. The method also includes dispensing the concentrated hair care composition from the dispenser, applying the concentrated hair care composition the hair; and rinsing the concentrated hair care composition from the hair.

Description

FIELD OF THE INVENTION

Described herein is a method of treating hair with a concentrated hair conditioning composition comprising an emulsifier system.

BACKGROUND OF THE INVENTION

Today's hair conditioners almost universally comprise high levels of high melting point fatty compounds, the most common of which are C16 to C18 fatty alcohols. These high melting point fatty compounds are employed as structuring agents wherein they are combined with one or more surfactants and an aqueous carrier to form a gel network. The gel network increases the viscosity and yield point which facilitates the dispensing of the conditioner from a bottle or tube and the subsequent distribution and spreading of the product through the hair by the consumer. The structuring of the product via gel network also enables incorporation of silicones, perfumes and oils in the form of an oil-in-water emulsion that is phase stable. These silicones and oils are intended to be deposited on the hair to provide the primary hair conditioning benefits including wet and dry combing friction reduction and improved hair manageability.
However, today's gel network hair conditioners can lead to excessive co-deposits of the high melting point fatty compound on the hair over multiple cycles. These co-deposits can lead to significant waxy build-up on hair and weight the hair down. Indeed, one of the major consumer complaints with hair conditioners is often waxy residue which can make hair look greasy or feel heavy. Many current gel network hair conditioners deposit up to 10 times more high melting point fatty compounds (fatty alcohols) than silicones or oils after approximately 10 treatment cycles in technical testing. While not being bound to theory, this is hypothesized to be due to the approximately 10x greater concentration of high melting point fatty compounds in the product relative to the silicone or oil. However, such a high level of melting point fatty compounds (fatty alcohols) has been required to produce a shelf stable gel network with sufficient structuring for consumer acceptable viscosity and rheology.
Described herein is a concentrated hair care composition that enables new product opportunities and consumer benefits by addressing the current disadvantages associated with gel network conditioners. It has been found that concentrated and ultra-low viscosity hair conditioner compositions can be delivered to the hair. These new compositions are concentrated to enable sufficient dosage while also substantially eliminating the need for high melting point fatty compounds or other “insoluble” structurants that can lead to significant co-deposits (from wax structured to gas structured), build-up and weigh down of hair. The new compositions can also comprise nano-emulsions to help enable shelf stability. The net result has been a step change improvement in silicone deposition purity versus today's rinse-off products and an improvement in technical performance benefits from such a pure and transparent deposited silicone layer. These benefits include multicycle hair conditioning without hair weigh down, durable conditioning, reduced hair dye fade, and increased color vibrancy.
Additionally, nanoemulsion technology development is hindered by complex stability issues that emerge when droplet sizes are driven to the nanoscale. This may be especially problematic in the presence of higher levels of perfume oils which may be required for such a concentrated product. The concentrated hair care composition described herein is therefore also focused on improved stability via the development of a specific emulsifier system.

SUMMARY OF THE INVENTION

Described herein is a method of treating the hair, the method comprising (a) providing a concentrated hair care composition in a dispenser, wherein the concentrated hair care composition comprises: (i) from about 3% to about 25% of one or more silicones, by weight of the concentrated hair care composition; (ii) from about 2% to about 10% high melting point fatty compounds, by weight of the concentrated hair care composition; (iii) from about 0.5% to about 7% perfume, by weight of the concentrated hair care composition; (iv) an emulsifier system comprising: (1) from about 1% to about 10% of one or more Type I emulsifiers by weight of the concentrated hair care composition, the one or more Type I emulsifiers having from about 5 to about 9 moles of ethoxylate, the one or more Type I emulsifiers having an HLB value of from about 10.3 to about 13; (2) from about 0.5% to about 5% of one or more Type II emulsifiers by weight of the concentrated hair care composition, the one or more Type II emulsifiers having from about 2 to about 4.9 moles of ethoxylate, the one or more Type II emulsifiers having an HLB value of from about 8 to about 10.3; and (v) from about 60% to about 90% water, by weight of the concentrated hair care composition; wherein the concentrated hair care composition has a liquid phase viscosity of from about 200 centipoise to about 15,000 centipoise; wherein the concentrated hair care composition has a silicone to high melting point fatty compound ratio of from about 80:20 to about 30:70, by weight of the silicone and by weight of the high melting point fatty compound; and wherein the concentrated hair care composition has a silicone to perfume ratio of from about 95:5 to about 50:50, by weight of the silicone and by weight of the perfume; (b) dispensing the concentrated hair care composition from the dispenser; (c) applying the concentrated hair care composition to the hair; and (d) rinsing the concentrated hair care composition from the hair.
Also described herein is a dispenser comprising a concentrated hair care composition, the concentrated hair care composition comprising: (a) from about 3% to about 25% of one or more silicones, by weight of the concentrated hair care composition, wherein the particle size of the one or more silicones is from about 1 nm to about 500 nm; (b) from about 2% to about 10% high melting point fatty compounds, by weight of the concentrated hair care composition; (c) from about 1% to about 7% perfume, by weight of the concentrated hair care composition; (d) an emulsifier system comprising: (i) from about 1% to about 10% of one or more Type I emulsifiers by weight of the concentrated hair care composition, the one or more Type I emulsifiers having from about 5 to about 9 moles of ethoxylate, the one or more Type I emulsifiers having an HLB value of from about 10.3 to about 13; (ii) from about 0.5% to about 5% of one or more Type II emulsifiers by weight of the concentrated hair care composition, the one or more Type II emulsifiers having from about 2 to about 4.9 moles of ethoxylate, the one or more Type II emulsifiers having an HLB value of from about 8 to about 10.3; and (e) from about 60% to about 90% water, by weight of the concentrated hair care composition; wherein the concentrated hair care composition has a liquid phase viscosity of from about 200 centipoise to about 15,000 centipoise; wherein the concentrated hair care composition has a silicone to high melting point fatty compound ratio of from about 80:20 to about 30:70, by weight of the silicone and by weight of the high melting point fatty compound; wherein the concentrated hair care composition has a silicone to perfume ratio of from about 95:5 to about 50:50, by weight of the silicone and by weight of the perfume; and wherein the concentrated hair care composition is rinse-off.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.
As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, “comprising” means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”.
As used herein, “mixtures” is meant to include a simple combination of materials and any compounds that may result from their combination.
As used herein, “molecular weight” or “M.Wt.” refers to the weight average molecular weight unless otherwise stated. As used herein, the terms “include,” “includes,” and “including,” are meant to be non-limiting and are understood to mean “comprise,” “comprises,” and “comprising,” respectively.
As used herein, the term “concentrated” means a hair care composition comprising from about 3% to about 25% of one or more silicones, by weight of the hair care composition.
As used herein, the term “nanoemulsion” means an oil-in-water (o/w) emulsion with an average particle size ranging from about 1 nm to about 100 nm. The particle size referred to herein is z-average measured by dynamic light scattering. The nanoemulsion described herein may be prepared by the following methods: (1) mechanically breaking down the emulsion droplet size; (2) spontaneously forming the emulsion (may be referred to as a microemulsion in the literature); and (3) using emulsion polymerization to achieve average particle size in the target range described herein.
All percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Hair Care Composition

The method of treating the hair described herein comprises providing a concentrated hair care composition in a dispenser. The concentrated hair care composition may comprise one or more silicones, perfume, an emulsifier system, and one or more fatty compounds.
A. Silicone Deposition Purity
The method of treating hair comprises applying a concentrated hair care composition to the hair. The concentrated hair care composition may comprise a silicone deposition purity of from about 30% to about 90%, alternatively from about 40% to about 80%, and alternatively from about 50% to about 70%, after applying the concentrated hair care composition to the hair and rinsing the concentrated hair care composition from the hair.
Deposition Purity can be determined by the ratio of silicone deposited per weight of hair to the total deposition of other ingredients per weight of hair. The amount of silicone is determined by either extraction or digestion of the hair followed by an analysis with a quantitative technique such as gas chromatography. The total deposition may be determined by the sum of separate deposition measurements or by a Single Inclusive Measurement of total deposition. The separate deposition measurements may include but are not limited to fatty alcohols, EGDS, quaternized agents, and silicone. Typically these measurements involve extracting the hair then separating the ingredients of interest with chromatography and quantifying with an externally calibration based on test solution concentration. The Single Inclusive Measurement of total deposition is gravimetric. The hair is thoroughly extracted and the residue determined by weighing the dissolved residue in the extract after evaporating the solvent. This residue contains both deposited ingredients and naturally occurring extractable compounds from the hair (primarily lipids). The naturally occurring extractable compounds are quantified and subtracted from the total. These include: fatty acids, squalene, cholesterol, ceramides, wax esters, triglycerides and sterol esters. The method of quantitation is similar to the deposition measurements. Other supporting evidence of Deposition Purity may include spectroscopic or topography mapping of the hair surface.
B. Silicones
The concentrated hair care composition may comprise from about 3% to about 25%, alternatively from about 5% to about 20%, alternatively from about 8% to about 18%, and alternatively from about 10% to about 14% of one or more silicones, by weight of the concentrated hair care composition. In a further embodiment, the hair care composition may comprise from about 3% to about 25%, alternatively from about 4% to about 20%, alternatively from about 5% to about 15% of one or more silicones, and alternatively from about 6% to about 12% by weight of the concentrated hair care composition. The particle size of the one or more silicones may be from about 1 nm to about 100 nm, alternatively from about 5 nm to about 80 nm, alternatively from about 10 nm to about 60 nm, and alternatively from about 12 nm to about 50 nm. In a further embodiment, the particle size of the one or more silicones may be from about 1 nm to about 500 nm, alternatively from about 5 nm to about 300 nm, alternatively from about 8 nm to about 200 nm, and alternatively from about 10 nm to about 100 nm. In an embodiment, the silicone is an aminosilicone comprising from about 0.7% to about 1.3% nitrogen content.
The particle size of the one or more silicones can be measured by dynamic light scattering (DLS) using the measurement angle and the refractive index of the one or more silicones. A Malvern Zetasizer Nano ZEN3600 system (www.malver.com) using He—Ne laser 633 nm can be used for the measurement at 25° C.
The Zetasizer Software provided by Malvern Instruments, was used for data analysis. For each sample, 3 measurements were made and Z-average values were reported as the particle size.
In an embodiment, the one or more silicones may be in the form of a nanoemulsion. A nanoemulsion, as defined herein, is an emulsion wherein the particle size is below 100 nm. The nanoemulsion may comprise any silicone suitable for application to the skin and/or hair. In one embodiment, from about 25% to about 100% of the one or more silicones is in the form of a nanoemulsion, in another embodiment from about 50% to about 100% of the one or more silicones is in the form of a nanoemulsion, and in another embodiument from about 75% to about 100% of the one or more silicones is in the form of a nanoemulsion.
In an embodiment, the one or more silicones may include in their molecular structure polar functional groups such as Si—OH (present in dimethiconols), primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. The one or more silicones may be selected from the group consisting of aminosilicones, pendant quaternary ammonium silicones, terminal quaternary ammonium silicones, amino polyalkylene oxide silicones, quaternary ammonium polyalkylene oxide silicones, and amino morpholino silicones.
The one or more silicones may comprise:

(a) at least one aminosilicone corresponding to formula (V):

R′_aG_3-a—Si(OSiG₂)_n—(OSiG_bR′_2-b)_m—O—SiG_3-a—R′_a (I)
in which:

G is chosen from a hydrogen atom, a phenyl group, OH group, and C₁-C₈alkyl groups, for example methyl,
a is an integer ranging from 0 to 3, and in one embodiment a is 0,
b is chosen from 0 and 1, and in one embodiment b is 1,
m and n are numbers such that the sum (n+m) can range for example from 1 to 2 000, such as for example from 50 to 150, wherein n can be for example chosen from numbers ranging from 0 to 1 999, such as for example from 49 to 149, and wherein m can be chosen from numbers ranging for example from 1 to 2 000, such as for example from 1 to 10;
R′ is a monovalent group of formula —C_qH_2qL in which q is a number from 2 to 8 and L is an optionally quaternized amine group chosen from the groups:

—NR″—CH₂—CH₂—N′(R¹)₂,
—N(R″)₂,
—N⁺(R″)₃A⁻,
—N⁺H(R″)₂A⁻,
—N⁺H₂(R″)A⁻, and
—N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,
in which R″ can be chosen from a hydrogen atom, phenyl groups, benzyl groups, and saturated monovalent hydrocarbon-based groups, such as for example an alkyl group comprising from 1 to 20 carbon atoms, and A⁺ is chosen from halide ions such as, for example, fluoride, chloride, bromide and iodide.
In an embodiment, the one or more silicones may include those corresponding to formula (1) wherein a=0, G=methyl, m and n are numbers such that the sum (n+m) can range for example from 1 to 2 000, such as for example from 50 to 150, wherein n can be for example chosen from numbers ranging from 0 to 1 999, such as for example from 49 to 149, and wherein m can be chosen from numbers ranging for example from 1 to 2 000, such as for example from 1 to 10; and L is —N(CH₃)₂or —NH₂, alternatively —NH₂.
Additional said at least one aminosilicone of the invention include:

(b) pendant quaternary ammonium silicones of formula (VII):

in which:

R₅is chosen from monovalent hydrocarbon-based groups comprising from 1 to 18 carbon atoms, such as C₁-C₁₈alkyl groups and C₂-C₁₈alkenyl groups, for example methyl;
R₆is chosen from divalent hydrocarbon-based groups, such as divalent C₁-C₁₈alkylene groups and divalent C₁-C₁₈alkylenoxy groups, for example C₁-C₈alkylenoxy groups, wherein said R₆is bonded to the Si by way of an SiC bond;
Q⁻ is an anion that can be for example chosen from halide ions, such as chloride, and organic acid salts (such as acetate);
r is an average statistical value ranging from 2 to 20, such as from 2 to 8;
s is an average statistical value ranging from 20 to 200, such as from 20 to 50.

Such aminosilicones are described more particularly in U.S. Pat. No. 4,185,087, the disclosure of which is incorporated by reference herein.
A silicone which falls within this class is the silicone sold by the company Union Carbide under the name “Ucar Silicone ALE 56”.
Further examples of said at least one aminosilicone include:

c) quaternary ammonium silicones of formula (VIIb):

in which:

groups R₇, which may be identical or different, are each chosen from monovalent hydrocarbon-based groups comprising from 1 to 18 carbon atoms, such as C₁-C₁₈alkyl groups, for example methyl, C₂-C₁₈alkenyl groups, and rings comprising 5 or 6 carbon atoms;
R₆is chosen from divalent hydrocarbon-based groups, such as divalent C₁-C₁₈alkylene groups and divalent C₁-C₁₈alkylenoxy, for example C₁-C₈, group connected to the Si by an SiC bond;
R₈, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based group comprising from 1 to 18 carbon atoms, and in particular a C₁-C₁₈alkyl group, a C₂-C₁₈alkenyl group or a group —R₆—NHCOR₇;
X⁻ is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.);
r represents an average statistical value from 2 to 200 and in particular from 5 to 100.
Such silicones are described, for example, in application EP-A-0 530 974, the disclosure of which is incorporated by reference herein.
Silicones falling within this class are the silicones sold by the company Goldschmidt under the names Abil Quat 3270, Abil Quat 3272 and Abil Quat 3474.
Further examples of said at least one aminosilicone include:
d) quaternary ammonium and polyalkylene oxide silicones
wherein the quaternary nitrogen groups are located in the polysiloxane backbone, at the termini, or both.
Such silicones are described in PCT Publication No. WO 2002/010257, the disclosure of which is incorporated by reference herein.
Siliciones falling within this class are the silicones sold by the company Momentive under the names Silsoft Q.
(e) Aminofunctional silicones having morpholino groups of formula (V):

in which
A denotes a structural unit (I), (II), or (III) bound via —O—
or an oligomeric or polymeric residue, bound via —O—, containing structural units of formulas (I), (II), or (III), or half of a connecting oxygen atom to a structural unit (III), or denotes —OH,

* denotes a bond to one of the structural units (I), (II), or (III), or denotes a terminal group B (Si-bound) or D (O-bound),
B denotes an —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃group,
D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃group,

a, b, and c denote integers between 0 and 1000, with the provision that a+b+c>0,
m, n, and o denote integers between 1 and 1000.
Aminofunctional silicones of this kind bear the INCI name:

Amodimethicone/Morpholinomethyl Silsesquioxane Copolymer. A particularly suitable amodimethicone is the product having the commercial name Wacker Belsil® ADM 8301E.

Examples of such silicones are available from the following suppliers:

- offered by the company Dow Corning:
  - Fluids: 2-8566, AP 6087, AP 6088, DC 8040 Fluid, fluid 8822A DC, DC 8803 & 8813 polymer, 7-6030, AP-8104, AP 8201;
  - Emulsions: CE-8170 AF Micro Emulsion, 2-8177, 2-8194

Microemulsion, 9224 Emulsion, 939, 949, 959, DC 5-7113 Quat Microemulsion, DC 5-7070 Emulsion, DC CE-8810, CE 8401 Emulsion, CE 1619, Dow Corning Toray SS-3551, Dow Corning Toray SS-3552;

- offered by the company Wacker:
  - Wacker Belsil ADM 652, ADM 656, 1100, 1600, 1650 (fluids) ADM 6060 (linear amodimethicone) emulsion; ADM 6057 E (branched amodimethicone) emulsion; ADM 8020 VP (micro emulsion); SLM 28040 (micro emulsion);
- offered by the Company Momentive:
  - Silsoft 331, SF1708, SME 253 & 254 (emulsion), SM2125 (emulsion), SM 2658 (emulsion), Silsoft Q (emulsion)
- offered by the company Shin-Etsu:
  - KF-889, KF-8675, KF-8004, X-52-2265 (emulsion);
- offered by the Company Siltech Silicones:
  - Siltech E-2145, E-Siltech 2145-35;
- offered by the company Evonik Industries:
  - Abil T Quat 60th

Some non-limiting examples of aminosilicones include the compounds having the following INCI names: Silicone Quaternium-1, Silicone Quaternium-2, Silicone Quaternium-3, Silicone Quaternium-4, Silicone Quaternium-5, Silicone Quaternium-6, Silicone Quaternium-7, Silicone Quaternium-8, Silicone Quaternium-9, Silicone Quaternium-10, Silicone Quaternium-11, Silicone Quaternium-12, Silicone Quaternium-15, Silicone Quaternium-16, Silicone Quaternium-17, Silicone Quaternium-18, Silicone Quaternium-20, Silicone Quaternium-21, Silicone Quaternium-22, Quaternium-80, as well as Silicone Quaternium-2 Panthenol Succinate and Silicone Quaternium-16/Glycidyl Dimethicone Crosspolymer.
In an embodiment, the aminosilicones can be supplied in the form of a nanoemulsion and include MEM 9049, MEM 8177, MEM 0959, MEM 8194, SME 253, and Silsoft Q.
In an embodiment, the one or more silicones may include dimethicones, and/or dimethiconols. The dimethiconols are hydroxyl terminated dimethylsilicones represented by the general chemical formulas
wherein R is an alkyl group (R may be methyl or ethyl, alternatively methyl) and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercial dimethiconols typically are sold as mixtures with dimethicone or cyclomethicone (e.g.,Dow Coming® 1401, 1402, and 1403 fluids).
C. Emulsifiers
The concentrated hair care compositions described herein can comprise a combination of from about 1% to about 10%, alternatively from about 2% to about 9%, and alternatively from about 3% to about 8% of one or more Type I emulsifiers, by weight of the concentrated hair care composition; and from about 0.5% to about 5.0%, alternatively from about 0.6% to about 4.5%, and alternatively from about 0.8% to about 4.0% of one or more Type II emulsifiers, by weight of the concentrated hair care composition.
The Type I emulsifiers can be chosen from alcohol ethoxylates which are condensation products of aliphatic alcohols having from about 10 to about 15 carbon atoms, in either straight chain or branched chain configuration, with from about 5 to about 9 moles of ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 5 to about 9 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atom. The aliphatic alcohol can be in the form of primary alcohol or secondary alcohol. The Type I emulsifiers have a range from about 10.3 to about 13.5, alternatively from 10.3 to 13.5, alternatively from about 10.3 to about 13, alternatively from 10.3 to 13. The HLB (hydrophilic-lipophilic balance) of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic.
The Type II emulsifiers can be chosen from alcohol ethoxylates which are condensation products of aliphatic alcohols having from about 10 to about 15 carbon atoms, in either straight chain or branched chain configuration, with from about 2 to about 4.9 moles of ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 2 to about 4.9 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atom. The aliphatic alcohol could be in either form of primary alcohol or secondary alcohol. In an embodiment, the Type II emulsifiers could also have from about 2 to 4,9 moles of ethylene oxide, alternatively from 2 to 4.9 moles of ethylene oxide. The Type II emulsifiers have a HLB range from about 8 to about 10.3, alternatively from 8 to 10.3.
Optionally, the concentrated hair care compositions described herein can comprise one or more Type III emulsifiers which may be present at from about 0% to about 3%, alternatively from about 0.5% to about 2.5 and alternatively from about 0.75% to about 1.5%, by weight of the concentrated hair care composition.
The Type III emulsifiers can be chosen from alcohol ethoxylates which are condensation products of aliphatic alcohols having from about 15 to about 20 carbon atoms, in either straight chain or branched chain configuration, with frog about 20 to about 200 moles of ethylene oxide, e.g., cetearyl alcohol ethylene oxide condensate having from about 20 to about 200 moles of ethylene oxide per mole of cetearyl alcohol, the alcohol chain having predominantly C16 to C18 chain lengths. The Type iii emulsifiers have an HLB range from about 16 to about 19.5, alternatively from 16 to 19 alternatively from about 16 to about 19. The addition of one or more Type III emulsifiers to the concentrated hair care compositions described herein can further enhance the stability of the concentrated hair care compositions described herein via steric interactions.
The HLB value for an individual emulsifier can be calculated using the following example method:
A typical nonionic emulsifier (e.g. Laureth-4) comprises an ethylene oxide groups or polyhydric alcohol hydrophilic portions with a fatty alcohol hydrophobic portion. The HLB for a nonionic surfactant can be calculated as follows:
Hydrophylic-lipohylic balance (HLB)
This value indicates the hydrophylic-lipophylic balance of a molecule and is calculated. theoretically:
$Ethoxylated fatty alcohols :$ $H L B = 20 \times (\frac{Moleculat weight of Hydrophilic part}{Molecular weight of molecule})$

EXAMPLE 1

HLB Calculation for Laureth-4

Molecular weight of ethoxylate portion=176
Molecular weight of lauryl alcohol=186
Wt. % Hydrophile=(176/(176+186))×100=48.6%
HLB=20×48.6/100=9.7

EXAMPLE 2

Calculation of HLB for a Surfactant Mixture

The surfactant mixture is a 70/30 blend of Steareth-2 and Steareth-21.
Total HLB:
Steareth-2 contribution 0.7×4.9=3.43
Steareth-21 contribution 0.3×15.5=4.65
Total HLB=8.08
Some exemplary emulsifiers:

C10 primary alcohol branched

	HLB	HC chain length	Mw

Imbentin-E/100/030 (3 EO)	8.5	10	290
Imbentin-E/100/050 (5 EO)	11.5	10	380
Imbentin-E/100/060 (6 EO)	12.5	10	420

C13 primary alcohol branched

	HLB	HC chain length	Mw

Imbentin-T/030 (3 EO)	8.1	13	330
Imbentin-T/040 (4 EO)	9	13	380
Imbentin-T/050 (5 EO)	10.6	13	420
Imbentin-T/060 (6 EO)	11.5	13	460

C11-15 Secondary alcohol

	HLB	HC chain length	Mw

C11-15 Pareth-5 (5 EO)	10.6	11-15	415
C11-15 Pareth-7 (7 EO)	12.1	11-15	515
C11-15 Pareth-9 (9 EO)	13.3	11-15	584
C11-15 Pareth-12 (12 EO)	14.5	11-15	738

The average HLB value for the combination of the one or more Type I emulsifiers and the one or rrrore Type II emulsifiers in the emulsifier system is from about 9.25 to about 13.25, alternatively from 9.25 to 13.25 based on the mole average. The mole average HLB value for the emulsifier mixture (HLB_mix) is calculated via solving the two following equations, concurrently:
$a : H L B_{mix} = \frac{w %_{EmI}}{{Mw}_{EmI}} \times H L B_{EmI} + \frac{w %_{EmII}}{{Mw}_{EmII}} \times H L B_{EmII}$ $b : \frac{w %_{EmI}}{{Mw}_{EmI}} + \frac{w %_{EmII}}{{Mw}_{EmII}} = 1$
wherein w % _EmIis the weight percentage for emulsifier Type I, Mw _EmIis the molecular weight for emulsifier Type I, w % _EmIIis the weight percentage for emulsifier Type II, Mw _EmIIis the molecular weight for emulsifier Type II.
For a target HLB_mixthe required w % for each emulsifier type can be calculated, as described in the following table:


				Target	Target
Type	EO#	HLB	Mw	HLB_mix: 11	HLB_mix: 12

Trideceth 9¹	EmI	9	13.2	601	71%	86%
Trideceth 3²	EmII	3	8	333	29%	14%

¹NOVEL TDA 9
²NOVEL TDA 3

D. Perfume
The concentrated hair care composition may comprise from about 1% to about 7%, alternatively from about 1.5% to about 6%, and alternatively from about 2% to about 5% perfume, by weight of the concentrated hair care composition.
In an embodiment, the concentrated hair care composition may have a silicone to perfume ratio of from about 95:5 to about 50:50, 90:10 to 60:40, 85:15 to 70:30.
Examples of suitable perfumes may be provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. A plurality of perfume components may be present in the concentrated hair care composition.
E. High Melting Point Fatty Compounds
The concentrated hair care composition may comprise from about 2% to about 10% high melting point fatty compounds, alternatively from about 4% to about 8% high melting point fatty compounds, alternatively from about 5% to about 7% high melting point fatty compounds, and alternatively may comprise about 6% high melting point fatty compounds, by weight of the concentrated hair care composition. In an embodiment, the concentrated hair care composition comprises from about 1.75% to about 8% fatty alcohols, alternatively from about 2% to about 6%, alternatively from about 2.25% to about 4%, and alternatively from about 2.5% to about 3.5%, by weight of the concentrated hair care composition. The concentrated hair care composition may have an oil to high melting point fatty compound ratio of from about 30:70 to about 80:20, alternatively from about 40:60 to about 70:30, and alternatively from about 50:50 to about 70:30 by weight of the oil and by weight of the high melting point fatty compound. In an embodiment, the concentrated hair care composition may have an oil to high melting point fatty compound ratio of from about 40:60 to about 85:15, alternatively from about 50:50 to about 80:20, and alternatively from about 55:45 to about 75:25 by weight of the oil and by weight of the high melting point fatty compound.
The high melting point fatty compounds have a melting point of about 25° C. or higher, and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. It is understood by the artisan that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification is not intended to be a limitation on that particular compound, but is done so for convenience of classification and nomenclature. Further, it is understood by the artisan that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than about 25° C. Such compounds of low melting point are not intended to be included in this section. Nonlimiting examples of the high melting point compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.
The fatty alcohols described herein are those having from about 14 to about 30 carbon atoms, alternativelyfrom about 16 to about 22 carbon atoms. These fatty alcohols are saturated and can be straight or branched chain alcohols. Nonlimiting examples of fatty alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.
The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, alternatively from about 12 to about 22 carbon atoms, and alternatively from about 16 to about 22 carbon atoms. These fatty acids are saturated and can be straight or branched chain acids. Also included are diacids, triacids, and other multiple acids which meet the requirements herein. Also included herein are salts of these fatty acids. Nonlimiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof.
The fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxy groups, hydroxy- substituted fatty acids, and mixtures thereof. Nonlimiting examples of fatty alcohol derivatives and fatty acid derivatives include materials such as methyl stearyl ether; the ceteth series of compounds such as ceteth-1 through ceteth-45, which are ethylene glycol ethers of cetyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; the steareth series of compounds such as steareth-1 through steareth-10, which are ethylene glycol ethers of steareth alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; ceteareth 1 through ceteareth-10, which are the ethylene glycol ethers of ceteareth alcohol, i.e., a mixture of fatty alcohols containing predominantly cetyl and stearyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; C16-C30 alkyl ethers of the ceteth, steareth, and ceteareth compounds just described; polyoxyethylene ethers of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, and mixtures thereof.
In an embodiment, the fatty compound may be a single high melting point compound of high purity. Single compounds of pure fatty alcohols selected may be selected from the group consisting of pure cetyl alcohol, stearyl alcohol, and behenyl alcohol. By “pure” herein, what is meant is that the compound has a purity of at least about 90%, alternatively at least about 95%.
Commercially available high melting point fatty compounds described herein include: cetyl alcohol, stearyl alcohol, and behenyl alcohol having tradenames KONOL series available from Shin Nihon Rika (Osaka, Japan), and NAA series available from NOF (Tokyo, Japan); pure behenyl alcohol having tradename 1-DOCOSANOL available from WAKO (Osaka, Japan), various fatty acids having tradenames NEO-FAT available from Akzo (Chicago, Ill. USA), HYSTRENE available from Witco Corp. (Dublin, Ohio USA), and DERMA available from Vevy (Genova, Italy).
F. Cationic Surfactants
In an embodiment, the concentrated hair care composition may comprise 0%, alternatively from about 0.25% to about 5%, alternatively from about 0.5% to about 4%, and alternatively from about 1% to about 3% cationic surfactants, by weight of the concentrated hair care composition.
The cationic surfactant may be a mono-long alkyl quaternized ammonium salt having the formula (XIII) [from WO2013148778]:
wherein one of R⁷¹, R⁷²R⁷³a n R⁷⁴selected from an aliphatic group of from about 14 to about 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30 carbon atoms; the remainder of R⁷¹, R⁷²R⁷³and R⁷⁴are independently selected from an aliphatic group of from about 1 to about 8 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 8 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, glutamate, and alkyl sulfonate radicals. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 16 carbons, or higher, can be saturated or unsaturated. In an embodiment, one of R⁷¹, R⁷²R⁷³and R⁷⁴is selected from an alkyl group of from about 14 to about 30 carbon atoms, alternatively from about 16 to about 22 carbon atoms, and alternatively from about 16 to about 18 carbon atoms; the remainder of R⁷¹, R⁷², R⁷³, and R⁷⁴are independently selected from the group consisting of CH₃, C₂H₅, C₂H₄OH, CH₂C₅H₅, and mixtures thereof; and (X) is selected from the group consisting of Cl, Br, CH₃OSO₃, and mixtures thereof. It is believed that such mono-long alkyl quatemized ammonium salts can provide improved slippery and slick feel on wet hair.
Nonlimiting examples of such mono-long alkyl quatemized ammonium salt cationic surfactants include: behenyl trimethyl ammonium chloride available, for example, with tradename Genamine KDMP from Clariant, with tradename INCROQUAT TMC-80 from Croda and ECONOL TM22 from Sanyo Kasei; stearyl trimethyl ammonium chloride available, for example, with tradename CA-2450 from Nikko Chemicals; cetyl trimethyl ammonium chloride available, for example, with tradename CA-2350 from Nikko Chemicals; behenyltrimethylammonium methyl sulfate, available from FeiXiang; hydrogenated tallow alkyl trimethyl ammonium chloride; stearyl dimethyl benzyl ammonium chloride; and stearoyl amidopropyl dimethyl benzyl ammonium chloride.
In an embodiment, the cationic surfactants are those having a shorter alkyl group, i.e., C₁₆alkyl group. Such cationic surfactant includes, for example, cetyl trimethyl ammonim chloride. It is believed that cationic surfactants having a shorter alkyl group are advantageous for concentrated hair care silicone nanoemulsion compositions of the present invention comprising a cationic surfactant and with improved shelf stability.
G. Water Miscible Solvents
The concentrated hair care composition described herein may comprise from about 0.1% to about 25%, alternatively from about 0.1% to about 20%, and alternatively from about 0.1% to about 15% of a water miscible solvent, by weight of the concentrated hair care composition. Non-limiting examples of suitable water miscible solvents include polyols, copolyols, polycarboxylic acids, polyesters and alcohols.
Examples of useful polyols include, but are not limited to, glycerin, diglycerin, propylene glycol, dipropylene glycol, ethylene glycol, butylene glycol, pentylene glycol, 1,3-butylene glycol, cyclohexane dimethanol, hexane diol, polyethylene glycol (200-600), sugar alcohols such as sorbitol, manitol, lactitol and other mono- and polyhydric low molecular weight alcohols (e.g., C₂-C₈alcohols); mono di- and oligo-saccharides such as fructose, glucose, sucrose, maltose, lactose, and high fructose corn syrup solids and ascorbic acid.
Examples of polycarboxylic acids include, but are not limited to citric acid, maleic acid, succinic acid, polyacrylic acid, and polymaleic acid.
Examples of suitable polyesters include, but are not limited to, glycerol triacetate, acetylated-monoglyceride, diethyl phthalate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate.
Examples of suitable dimethicone copolyols include, but are not limited to, PEG-12 dimethicone, PEG/PPG-18/18 dimethicone, and PPG-12 dimethicone.
Examples of suitable alcohols include, but are not limited to ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol.
Other suitable water miscible solvents include, but are not limited to, alkyl and allyl phthalates; napthalates; lactates (e.g., sodium, ammonium and potassium salts); sorbeth-30; urea; lactic acid; sodium pyrrolidone carboxylic acid (PCA); sodium hyraluronate or hyaluronic acid; soluble collagen; modified protein; monosodium L-glutamate; alpha & beta hydroxyl acids such as glycolic acid, lactic acid, citric acid, maleic acid and salicylic acid; glyceryl polymethacrylate; polymeric plasticizers such as polyquaterniums; proteins and amino acids such as glutamic acid, aspartic acid, and lysine; hydrogen starch hydrolysates; other low molecular weight esters (e.g., esters of C₂-C₁₀alcohols and acids); and any other water soluble plasticizer known to one skilled in the art of the foods and plastics industries; and mixtures thereof.
In an embodiment, the water miscible solvents may be selected from the group consisting of glycerin, propylene glycol, dipropylene glycol, and mixtures thereof. EP 0283165 B1 discloses other suitable water miscible solvents, including glycerol derivatives such as propoxylated glycerol.
H. Viscosity Modifiers
The concentrated hair care composition described herein may comprise from about 0.1% to about 2%, alternatively from about 0.1% to about 1%, and alternatively from about 0.1% to about 0.5% of a viscosity modifier, by weight of the concentrated hair care composition. Non-limiting examples of suitable viscosity modifiers include water soluble polymers, cationic water soluble polymers,
Examples of water soluble polymers include, but are not limited to (1) vegetable based polymers such as gum Arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, algal colloid, starch (rice, corn, potato, or wheat), and glycyrrhizinic acid; (2) microorganism-based polymers such as xanthan gum, dextran, succinoglucan, and pullulan; and (3) animal-based polymers such as collagen, casein, albumin, and gelatin. Examples of semi-synthetic water-soluble polymers include (1) starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; (2) cellulose-based polymers such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose (CMC), crystalline cellulose, and cellulose powder; and (3) alginate-based polymers such as sodium alginate and propylene glycol alginate. Examples of synthetic water-soluble polymers include (1) vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether- based polymer, polyvinylpyrrolidone, and carboxyvinyl polymer (CARBOPOL 940, CARBOPOL 941; (2) polyoxyethylene-based polymers such as polyethylene glycol 20,000, polyethylene glycol 6,000, and polyethylene glycol 4,000; (3) copolymer-based polymers such as a copolymer of polyoxyethylene and polyoxypropylene, and PEG/PPG methyl ether; (4) acryl-based polymers such as poly(sodium acrylate), poly(ethyl acrylate), polyacrylamide, polyethylene imines, and cationic polymers. The water-swellable clay minerals are nonionic water-soluble polymers and correspond to one type of colloid-containing aluminum silicate having a triple layer structure. More particular, as examples thereof, mention may be made of bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, aluminum magnesium silicate, and silicic anhydride.
Examples of cationic water soluble polymers include, but are not limited to (1) quaternary nitrogen-modified polysaccharides such as cation-modified cellulose, cation-modified hydroxyethylcellulose, cation-modified guar gum, cation-modified locust bean gum, and cation-modified starch; (2) dimethyldiallylammonium chloride derivatives such as a copolymer of dimethyldiallylammonium chloride and acrylamide, and poly(dimethylmethylene piperidinium chloride); (3) vinylpyrrolidone derivatives such as a salt of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylic acid, a copolymer of vinylpyrrolidone and methacrylamide propyltrimethylammonium chloride, and a copolymer of vinylpyrrolidone and methylvinylimidazolium chloride; and (4) methacrylic acid derivatives such as a copolymer of methacryloylethyldimethylbetaine, methacryloylethyl trimethylammonium chloride and 2-hydroxyethyl methacrylate, a copolymer of methacryloylethyldimethylbetaine, and methacryloylethyl trimethylammonium chloride and methoxy polyethylene glycol methacrylate.
I. Viscosity
The concentrated hair care composition described herein may have a liquid phase viscosity of from about 200 centipoise to about 5,000 centipoise, alternatively from about 300 centipoise to about 4,000 centipoise, alternatively from about 400 centipoise to about 3,000 centipoise, and alternatively from about 500 centipoise to about 2,000 centipoise. In one embodiment, the concentrated hair care composition described herein may have a liquid phase viscosity of from about 200 centipoise to about 15,000 centipoise, alternatively from about 300 centipoise to about 10,000 centipoise, alternatively from about 400 centipoise to about 7,500 centipoise, alternatively from about 500 centipoise to about 5,000 centipoise, and alternatively from about 600 centipoise to about 3,000 centipoise.
The viscosity values may be measured employing any suitable rheometer or viscometer at 25.0° C. and at a shear rate of about 2 reciprocal seconds. The viscosities reported herein were measured using a Cone/Plate Controlled Stress Brookfield Rheometer R/S Plus, by Brookfield Engineering Laboratories, Stoughton, Mass. The cone used (Spindle C-75-1) has a diameter of 75 mm and 1° angle. The viscosity is determined using a steady state flow experiment at constant shear rate of 2 s⁻¹and at temperature of 25.0° C. The sample size is 2.5 ml and the total measurement reading time is 3 minutes.
J. Optional Ingredients
The concentrated hair care composition described herein may optionally comprise one or more additional components known for use in hair care or personal care products, provided that the additional components are physically and chemically compatible with the essential components described herein, or do not otherwise unduly impair product stability, aesthetics or performance. Such optional ingredients are most typically those materials approved for use in cosmetics and that are described in reference books such as the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992. Individual concentrations of such additional components may range from about 0.001 wt % to about 10 wt % by weight of the conditioning composition.
Emulsifiers suitable as an optional ingredient herein include mono- and di-glycerides, fatty alcohols, polyglycerol esters, propylene glycol esters, sorbitan esters and other emulsifiers known or otherwise commonly used to stabilized air interfaces, as for example those used during preparation of aerated foodstuffs such as cakes and other baked goods and confectionary products, or the stabilization of cosmetics such as hair mousses.
Further non-limiting examples of such optional ingredients include preservatives, perfumes or fragrances, cationic polymers, viscosity modifiers, coloring agents or dyes, conditioning agents, hair bleaching agents, thickeners, moisturizers, foam boosters, additional surfactants or nonionic cosurfactants, emollients, pharmaceutical actives, vitamins or nutrients, sunscreens, deodorants, sensates, plant extracts, nutrients, astringents, cosmetic particles, absorbent particles, adhesive particles, hair fixatives, fibers, reactive agents, skin lightening agents, skin tanning agents, anti-dandruff agents, perfumes, exfoliating agents, acids, bases, humectants, enzymes, suspending agents, pH modifiers, hair colorants, hair perming agents, pigment particles, anti-acne agents, anti-microbial agents, sunscreens, tanning agents, exfoliation particles, hair growth or restorer agents, insect repellents, shaving lotion agents, non-volatile solvents or diluents (water-soluble and water-insoluble), co-solvents or other additional solvents, and similar other materials.
K. Dispenser
The dispenser described herein may be any suitable dispenser for dispensing the concentrated hair composition. In an embodiment, the bottle may comprise a flip-top or a disc-top closure with an orifice opening. The dispenser may be a bottle comprising a substantially rigid wall. A substantially rigid wall may mean that the walls of the bottle to not collapse under atmospheric pressure. In an embodiment, the dispenser may comprise a neck narrower than the body. In an embodiment, the dispenser may be made of a material comprising polypropylene plastic. In an embodiment, the dispenser may comprise a closure that is threaded or snap-on.
In an embodiment, the dispenser may comprise a closure comprising an elastomeric valve. In an embodiment, the elastomeric valve may be cross-slit. The elastomeric valve may be seated in the closure and may be combined with a flip-top cap. The elastomeric valve may be made of a material selected from the group consisting of silicone, rubber, synthetic rubber, and combinations thereof. Other suitable valve designs may include duck-bill valves and dome valves.
In an embodiment, the dispenser may comprise a pump mechanism involving a dip tube to enable upright dosing.
The concentrated hair care composition is dispensed at a dosage weight of from about 1 g to about 10 g, alternatively from about 1 g to about 8 g, and alternatively from about 1 g to about 5 g. In an embodiment, the concentrated hair care composition is dispensed at a dosage weight of from about 1 g to about 7 g when dispensed from the dispenser, alternatively from about 2 g to about 6 g, alternatively from about 2.5 g to about 5 g, and alternatively from about 3 g to about 4.5 g. The dosage may be obtained via a single squeeze, pump or actuation of the dispenser, but may be accomplished via two squeezes, pumps or actuations of the dispenser.
I. Water
The concentrated hair care composition described herein may comprise from about from about 60% to about 90% water, alternatively from about 65% to about 87.5%, alternatively from about 67.5% to about 85%, alternatively from about 70% to about 82.5%, and alternatively from about 72.5% to about 80% water.

Method of Treating Hair

The method of treating the hair described herein comprises (1) providing a concentrated hair care composition in a dispenser, (2) dispensing the concentrated hair composition, (3) applying the concentrated hair care composition to the hair; and (4) rinsing the concentrated hair care composition from the hair.

EXAMPLES & DATA

The following examples and comparative examples are provided to help illustrate the concentrated hair care composition described herein. The exemplified compositions can be prepared by conventional formulation and mixing techniques. It will be appreciated that other modifications of the concentrated hair care compositions described herein within the skill of those in the emulsion formulation art can be undertaken without departing from the spirit and scope of this invention. All parts, percentages, and ratios herein are by weight unless otherwise specified. Some components may come from suppliers as dilute solutions. The amount stated reflects the weight percent of the active material, unless otherwise specified.
The emulsification route described herein is “Low-Energy Route” in which the aqueous emulsion in formed by phase inversion by composition (PIC)^1,2. In this route water or acidified water is added to the mixture of silicone and emulsifiers.
The concentrated hair care compositions described herein are of two types; one without gel network and the other with gel network.
The following tables describe comparative examples for the silicone emulsions prepared under the following conditions:
a. The emulsions containing only Type I emulsifier
b. The emulsions containing only Type II emulsifier
c. The emulsions containing Type I and Type I emulsifiers
d. The emulsions containing Type II and Type II emulsifiers
Examples of Type I and Type II emulsifiers are provided below.
a. The emulsions containing only one Type I emulsifier

TABLE 1

comparative example 1a

	Amodimethicone ¹	20.00
	Trideceth 5 ²	10.00
	Glycerin	0.00
	Water	Q.S.
	pH	9.8

	Particle Size (PS): 326 nm
	¹Salager et al., J Disp. Sci & Tech. 4, 313, 83
	²Sajjadi, Langmuir, 22, 5597, 2006
	¹Y17045-Momentive
	²Synpronic 13/5-LQ-(HLB: 11, EO: 5)

TABLE 2

Comparative example 1b

	Amodimethicone ¹	20.00
	Trideceth 5 ²	10.00
	Glycerin	0.00
	Glacial acetic acid	1.00
	Water	Q.S.
	pH	8.0

	Observation: Very high viscosity (Gelled)
	¹Y17045-Momentive
	²Synpronic 13/5-LQ-(HLB: 11, EO: 5)

TABLE 3

Comparative example 2a

	Amodimethicone ¹	20.00
	C11-15 pareth 9 ²	10.00
	Glycerin	0.00
	Glacial acetic acid	1.00
	Water	Q.S.
		PS: 249 nm

	¹Y17045-Momentive
	²Tergitol 15-s-9 (HLB: 13.3, EO: 9)

TABLE 4

Comparative example 2b

	Amodimethicone ¹	20.00
	C11-15 pareth 9 ²	10.00
	Glycerin	1.50
	Glacial acetic acid	1.00
	Water	Q.S.
		PS: 228 nm

	¹Y17045-Momentive
	²Tergitol 15-s-9 (HLB: 13.3, EO: 9)

b. The emulsions containing only one Type II emulsifier

TABLE 5

Comparative example 3

	Amodimethicone ¹	20.00
	Trideceth 3 ²	10.00
	Glycerin	0.00
	Glacial acetic acid	1.00
	Water	Q.S.
		PS: 256 nm

	¹Y17045-Momentive
	²Iconol TDA 3 (HLB: 8, EO: 3)

TABLE 6

Comparative example 4 and 5

Comparative Example	4	5

Amodimethicone ¹	20.00	20.00
Deceth 4	10.00	8.00
Glycerin	1.50	1.50
Glacial acetic acid	1.00	1.00
Water	Q.S.	Q.S.
	PS: 287 nm	PS: 326 nm

¹Y17045-Momentive
²Imbentin-E/100/040 (HLB: 10, EO: 4)

TABLE 7

Comparative Example 6

	Amodimethicone ¹	20.00
	Laureth 4 ²	10.00
	Glycerin	0.00
	Glacial acetic acid	1.00
	Water	Q.S.
		PS: 246 nm

	¹Y17045-Momentive
	²Dehydol LS 4 DEO-N (HLB: 9, EO: 4)

c. The Emulsions Containing a Combination of Type I Emulsifiers

TABLE 8

Comparative example 7

	Amodimethicone ¹	20.00
	C11-15 Pareth 7 ²	7.73
	C11-15 Pareth 9 ³	2.27
	Glycerin	1.50
	Glacial acetic acid	1.00
	Water	Q.S.
		PS: 59 nm

	¹Y17045-Momentive
	²Tergitol 15-s-9 (HLB: 13.3, Mw: 584 g/mol)
	³Tergitol 15-s-7 (HLB: 12.1, Mw: 515 g/mol)

The emulsion given in comparative example 7 (Table 8), gives a particle size below 100 nm; however, once the emulsion is incorporated into the conditioner formulation given in the comparative example 8, the formulation becomes unstable as evidenced by the increase in the particle size.
d. The Emulsions Containing a Combination of Type II Emulsifiers

TABLE 10

Comparative examples 9-11

Comparative
Example	9	10	11

Amodimethicone ¹	20.00	20.00	20.00
Deceth 2 ²	0	0.44	0
Deceth 2.5 ³	0.71	0.00	0.00
Deceth 3 ⁴	0	0	0.88
Deceth 4 ⁵	9.29	9.56	9.12
Glycerin	1.50	1.50	1.50
Glacial acetic acid	1.00	1.00	1.00
Water	Q.S.	Q.S.	Q.S.
	PS: 239 nm	PS: 356 nm	PS: 294 nm

¹Y17045-Momentive
²Imbentin-AG/100/020 (HLB: 7.2, Mw: 240 g/mol)
³Greenbentin DE/025 (HLB: 8.2, Mw: 268 g/mol)
⁴Imbentin-E/100/030 (HLB: 8.5, Mw: 290 g/mol)
⁵Imbentin-E/100/040 ( HLB: 10.0, Mw: 330 g/mol)

1. Conditioner Formulations with Gel Network
The comparative examples described herein are for conditioner formulations containing gel network. The measurement parameter for these compositions is viscosity which correlates with the gel network structure (i.e. The more disruption in gel network structure, the lower the viscosity of the conditioner composition).

TABLE 10

Comparative example 11.
Comparative example 11 comprising a commercial emulsion
using a combination of only Type I emulsifiers.

	Raw Material	% w

	Distilled Water	Q.S.
	Disodium EDTA	0.127
	BTMS/IPA	5.3315
	Cetyl Alcohol	0.8635
	Stearyl Alcohol	2.1545
	Benzyl Alcohol	0.4
	Kathon CG	0.0333
	Amodimethicone emulsion (20% active) ¹	40
	Perfume	2
	Citric acid	0.02
	Viscosity (cp)	<300

	Silsoft 253 (INCI: Amodimethicone (and) C11-15 Pareth-7 (and) Laureth-9 (and) Glycerin 1 (and) Trideceth-12)

TABLE 11

Comparative examples 12 and 13
Comparative example 12 and 13 comprising silicone emulsions
using a combination of only Type I emulsifiers.

Comparative Example	12	13
Raw Material	% w	% w

Distilled Water	Q.S.	Q.S.
Disodium EDTA	0.13	0.13
Behentrimonium Methosulfate Isopropyl Alcohol	5.33	5.33
Cetyl Alcohol	0.86	0.86
Stearyl Alcohol	2.15	2.15
Perfume	2.00	0.00
C11-15 Pareth 9 ¹	2.56	2.56
C11-15 Pareth 12 ²	0.00	2.14
Laureth 9 ³	1.20	1.00
Trideceth 12 ⁴	0.24	0.30
Glycerin	1.20	1.20
Amodimethicone ⁵	8.00	8.00
Benzyl Alcohol	0.40	0.40
Kathon CG	0.03	0.03
Citric acid	0.02	0.02
Viscosity (cp)	<300	<300

¹Tergitol 15-s-9 (HLB: 13.3, Mw: 584 g/mol)
²Tergitol 15-s-12 (HLB: 14.5, Mw: 738 g/mol)
³Brij L9 (HLB: 13.6, Mw: 580 g/mol)
⁴Novel TDA-12 (HLB: 14.4, Mw: 729 g/mol)
⁵Y17045-Momentive

The following table provides+examples of the conditioner formulations in which the gel network has not been compromised (reduced viscosity) to the extent of comparative examples 21-23, as evidenced by the viscosity values of conditioner formulations.

TABLE 13

Examples for conditioner formulations containing gel network

Example

	14	15	16	17	18	19
Raw Material	% w	% w	% w	% w	% w	% w

Distilled Water	Q.S.	Q.S.	Q.S.	Q.S.	Q.S.	Q.S.
Disodium EDTA	0.13	0.13	0.13	0.13	0.13	0.13
Behentrimonium Methosulfate	5.33	5.33	5.33	5.33	5.33	5.33
Isopropyl Alcohol
Cetyl Alcohol	0.86	0.86	0.86	0.86	0.86	0.86
Stearyl Alcohol	2.15	2.15	2.15	2.15	2.15	2.15
Perfume	2.00	2.00	2.00	2.00	2.00	2.00
C11-15 Pareth 7¹	2.56	0	0	0	0	0
Trideceth 5²	0.00	2.18	2.18	2.18	0	0
Trideceth 3³	0.00	1.22	1.22	0	0	0
C12-13 Pareth-3⁴	0.00	0	0	1.22	0	0
Ceteareth 25⁵	0.00	0	0.6	0.6	0	0.6
Steareth 100⁶	0.00	0.6	0	0	0.6	0
Deceth-3⁷	1.44	0.00	0.00	0.00	0.00	0.00
C11-15 Pareth 5⁸	0.00	0.00	0.00	0.00	2.18	2.18
Trideceth 4⁹	0.00	0.00	0.00	0.00	1.22	1.22
Glycerin	1.20	1.20	1.20	1.20	1.20	1.20
Amodimethicone¹⁰	8.00	8.00	8.00	8.00	8.00	8.00
Benzyl Alcohol	0.40	0.40	0.40	0.40	0.40	0.40
Kathon CG	0.03	0.03	0.03	0.03	0.03	0.03
Citric acid	0.02	0.02	0.02	0.02	0.02	0.02
Viscosity (cp)	851	812	740	852	1483	1077

¹Tergitol 15-s-7 (HLB: 12.1, Mw: 515 g/mol)
²Novel TDA-5 (HLB: 10.4, Mw: 421 g/mol)
³Iconol TDA 3 (HLB: 8, Mw: 333 g/mol)
⁴Brij LT-3 (HLB: 8, Mw: 333 g/mol)
⁵Cremophor A 25 (HLB: 16.2, Mw: 1360 g/mol)
⁶Brij S100 (HLB: 18.8), Mw: 4670 g/mol)
⁷Imbentin-E/100/030 (HLB: 8.5, Mw: 290 g/mol)
⁸Tergitol 15-s-5 (HLB: 10.6, Mw: 415 g/mol)
⁹Imbentin T-40 (HLB: 9, Mw: 380 g/mol)
¹⁰Y 17045-Momentive

The impact of emulsifier on the gel network is believed to be due to moles of ethylene oxide in the emulsifier (i.e. EO #). To demonstrate such an impact and define the optimum EO number for the formulation, emulsifiers of different EO moles is introduced into the conditioner formulation individually at 2 and 4%, according to the Table 13. The corresponding emulsifier systems evaluated in conditioning formulations for their impact on the viscosity of the conditioner and its stability are provided in Tables 14 (for primary ethoxylated alcohol emulsifiers) and 150 (for secondary ethoxylated alcohol emulsifiers).

TABLE 13

Conditioner compositions formulated with two different emulsifier
levels of 2 and 4%

	20	21
	With 4% emulsifier	With 2% emulsifier
Ingredients	% w	% w

Disodium EDTA	0.13	0.13
BTMS/IPA	5.33	5.33
Cetyl Alcohol	0.86	0.86
Stearyl Alcohol	2.15	2.15
Benzyl Alcohol	0.40	0.40
Kathon CG	0.03	0.03
Citric acid	0.02	0.02
Perfume	2.00	2.00
Emulsifier	4.00	2.00
Water	QS	QS

The viscosity values of the formulations measured on the 2^ndday are given in the Table 2 for emulsifiers of primary ethoxylated alcohol type and with a hydrocarbon chain range of 11-14 carbons. As can be seen from Table 14, the viscosity of the compositions significantly decrease when the EO moles of emulsifier increases from 6 to 10.

TABLE 14

Viscosity values for conditioners containing primary ethoxylated
alcohol emulsifiers at 2 and 4%.

				Viscosity	Viscosity
				(cp)	(cp)
	Hydrocarbon	EO	Commercial	4%	2%
HLB	chain	moles	name	emulsifier	emulsifier

8	11-14 (13 rich)	3	BASF TDA-3	7345	5165
8.1	11-14 (13 rich)	3	Imbentin T/30	7908	5243
8	13	3	Novel TD3	8617	4779
8	11-14 (13 rich)	4	Imbentin T/040	8492	5354
10.4	13	5	Novel TDA-5	8904	5291
10.6	11-14 (13 rich)	5	Imbentin T/050	8262	4993
11	13	5	Synperonic 13/5	8432	4952
11.3	13	6	Hetoxol TD-6	6695	4624
11.3	13	6	Novel TD6	5791	4740
11.5	11-14 (13 rich)	6	Imbentin T/060	8187	4828
13.9	11-14 (13 rich)	10	Imbentin T/100	1617	2652
15.4	11-14 (13 rich)	15	Imbentin T/150	2482	2731
16	13	18	Hetoxol TD-18	2210	3495

Viscosity for the conditioner formulation without any emulsifier: 5876 cp

Also, Table 15 provides the viscosity values of the conditioner formulations (measured on the 2^ndday) comprising emulsifiers of secondary ethoxylated alcohol type and with a hydrocarbon chain range of 11-15 carbons. As can be seen from Table 15, the viscosity of the conditioner compositions significantly decrease when the EO moles of emulsifier increases from 9 to 12.

TABLE 15

Viscosity values for conditioners containing secondary
ethoxylated alcohol emulsifiers at 2 and 4%.

				Viscosity	Viscosity
	HC chain	EO		(cp)	(cp)
HLB	length	number	Emulsifier	4%	2%

8	12-13	3	BriJ LT-3	8044	4698
8	11-15	3	15-s-3	6102	4701
10.6	11-15	5	15-s-5	8325	5755
12.1	11-15	7	15-s-7	3336	2297
12	12-14	7	Nikkol BT-7	3057	2124
13.3	11-15	9	15-s-9	783	2509
13.5	12-14	9	Nikkol BT-9	1165	2672
14.5	11-15	12	Tergitol 15-S-12	875	2145
14.5	12-14	12	Nikkol BT-12	1430	1093
15	12-13	12	Brij LT-12	2057	2943
16.3	11-15	20	Tergitol 15-S-20	2960	4189

Viscosity for the conditioner formulation without any emulsifier: 5876 cp

The viscosity values for conditioner compositions containing emulsifiers with longer hydrocarbon chain length (16-18) with HLB values greater than 16 are given in Table 16. According to the data provided in Table 4, these emulsifiers do not negatively impact (that is, do not reduce) the viscosity of the conditioner composition, and the emulsifiers described herein can assist with maintaining the viscosity of conditioner formulation.

TABLE 161

Viscosity values for conditioners containing emulsifiers of ceteareth
and steareth at 2 and 4%. This class of emulsifiers are Type III
(containing a long carbon chain (C15-C20) and higher moles of EO
(20-200) in their molecule

	HC chain	EO		Viscosity	Viscosity
HLB	length	number	Emulsifier	4%	2%

16.2	16-18	25	Ceteareth 25	4981	6457
17.7	16-18	50	Ceteareth 50	5180	6210
18.8	18	100	Steareth 100	6690	7561

Viscosity for the conditioner formulation without any emulsifier: 5876 cp

TABLE 17

The emulsions comprising Type I, Type II and Type III emulsifiers.

Example	22	23	24

Amodimethicone¹	20	20	20
Glycerin	1	3	3
Trideceth-3	0.72	3.48	3.7
Ceteareth-25	1.5	1.5	4.3
C11-15 Pareth 7 ²		5.02	2
C11-15 Pareth 9 ³	7.78
acetic acid	2	1.66	1.66
Phenoxy Ethanol	1
Water	(q.s.)	(q.s.)	(q.s.)
HLB	12.8	10.3	10.3

¹Y17045 available from Momentive
²Tergitol 15-S-9 (HLB 13.3, MW 584 g/mol)
³Tergitol 15-S-7 (HLB 12.1, MW 515 g/mol)

TABLE 18

Conditioner compositions comprising Type I, Type II and
Type III emulsifiers

Raw Material	25	26	27	28	29
Aminofunctional	7.6
polydimethylsiloxane
emulsion¹
Amodimethicone		7.6
emulsion²
Aminosilicone			7.6
emulsion Ex 32
Aminosilicone				7.6
emulsion Ex 33
Aminosilicone					7.6
emulsion Ex 34
Perfume	1.9	1.9	1.9	1.9	1.9
Behentrimonium	4.05	4.05	4.05	4.05	4.05
Methosulfate -
Isopropyl Alcohol
Cetyl Alcohol	0.82	0.82	0.82	0.82	0.82
Stearyl Alcohol	2.04	2.04	2.04	2.04	2.04
Disodium EDTA	0.12	0.12	0.12	0.12	0.12
Benzyl alcohol	0.38	0.38	0.38	0.38	0.38
Citric acid	0.02	0.02	0.02	0.02	0.02
Preservative	0.03	0.03	0.03	0.03	0.03
(Kathon)
Water	(q.s.)	(q.s.)	(q.s.)	(q.s.)	(q.s.)

¹Commercially available Belsil ADM-8301E from Wacker Silicone
²Commercially available Silsoft 253 from Momentive

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

What is claimed is:

1) A method of treating the hair, the method comprising:

a) providing a concentrated hair care composition in a dispenser, wherein the concentrated hair care composition comprises:

i) from about 3% to about 25% of one or more silicones, by weight of the concentrated hair care composition;

ii) from about 2% to about 10% high melting point fatty compounds, by weight of the concentrated hair care composition;

iii) from about 0.5% to about 7% perfume, by weight of the concentrated hair care composition;

iv) an emulsifier system comprising:

a) from about 1% to about 10% of one or more Type I emulsifiers by weight of the concentrated hair care composition, the one or more Type I emulsifiers having from about 5 to about 9 moles of ethoxylate, the one or more Type I emulsifiers having an HLB value of from about 10.3 to about 13;

b) from about 0.5% to about 5% of one or more Type II emulsifiers by weight of the concentrated hair care composition, the one or more Type II emulsifiers having from about 2 to about 4.9 moles of ethoxylate, the one or more Type II emulsifiers having an HLB value of from about 8 to about 10.3; and

v) from about 60% to about 90% water, by weight of the concentrated hair care composition;

wherein the concentrated hair care composition has a liquid phase viscosity of from about 200 centipoise to about 15,000 centipoise;

wherein the concentrated hair care composition has a silicone to high melting point fatty compound ratio of from about 80:20 to about 30:70, by weight of the silicone and by weight of the high melting point fatty compound; and

wherein the concentrated hair care composition has a silicone to perfume ratio of from about 95:5 to about 50:50, by weight of the silicone and by weight of the perfume;

b) dispensing the concentrated hair care composition from the dispenser;

c) applying the concentrated hair care composition to the hair; and

d) rinsing the concentrated hair care composition from the hair.

2) The method of claim 1, wherein the one or more silicones has a particle size of from about 1 nm to about 500 nm.

3) The method of claim 1, wherein the concentrated hair care composition has a liquid phase viscosity of from about 300 centipoise to about 10,000 centipoise.

4) The method of claim 1, wherein the one or more silicones are selected from aminosilicones, pendant quaternary ammonium silicones, terminal quaternary ammonium silicones, amino polyalkylene oxide silicones, quaternary ammonium polyalkylene oxide silicones, amino morpholino silicones, and mixtures thereof.

5) The method of claim 1, wherein the concentrated hair care composition comprises from about 4% to about 20% of one or more silicones, by weight of the concentrated hair care composition.

6) The method of claim 1, wherein the concentrated hair care composition comprises from about 2% to about 12% of a nonionic emulsifier, by weight of the concentrated hair care composition.

7) The method of claim 1, wherein the silicone is an aminosilicone comprising from about 0.7% to about 1.3% nitrogen content.

8) The method of claim 1, wherein the concentrated hair care composition has a silicone to high melting point fatty compound ratio of from about 40:60 to about 70:30.

9) The method of claim 1, wherein the particle size of the one or more silicones is from about 10 nm to about 100 nm.

10) The method of claim 1, wherein the concentrated hair care composition is a nanoemulsion.

11) The method of claim 1, wherein from about 25% to about 100% of the one or more silicones is in the form of a nanoemulsion, by weight of the concentrated hair care composition.

12) The method of claim 1, wherein the concentrated hair care composition comprises a silicone deposition purity of from about 30% to about 90% after applying the concentrated hair care composition to the hair and rinsing the concentrated hair care composition from the hair.

13) The method of claim 1, wherein the concentrated hair care composition comprises from about 5% to about 15% of the one or more silicones, by weight of the concentrated hair care composition.

14) The method of claim 1, wherein the concentrated hair care composition comprises from about 4% to about 8% high melting point fatty compounds, by weight of the concentrated hair care composition.

15) The method of claim 1, wherein the concentrated hair care composition comprises from about 2.25% to 4% high melting point fatty compounds, by weight of the concentrated hair care composition, and the silicone to high melting point fatty compound ratio is from about 50:50 to about 80:20.

16) The method of claim 1, wherein the concentrated hair care composition comprises from about 1.5% to about 6% perfume, by weight of the concentrated hair care composition.

17) The method of claim 1, wherein the concentrated hair care composition comprises from about 2% to about 5% perfume, by weight of the concentrated hair care composition.

18) The method of claim 1, wherein the concentrated hair care composition has a dosage weight of from about 2.5 g to about 5 g.

19) The method of claim 1, wherein the concentrated hair care composition has a density of about 1 g/cm³.

20) A dispenser comprising a concentrated hair care composition, the concentrated hair care composition comprising:

a) from about 3% to about 25% of one or more silicones, by weight of the concentrated hair care composition, wherein the particle size of the one or more silicones is from about 1 nm to about 500 nm;

b) from about 2% to about 10% high melting point fatty compounds, by weight of the concentrated hair care composition;

c) from about 1% to about 7% perfume, by weight of the concentrated hair care composition;

d) an emulsifier system comprising:

i) from about 1% to about 10% of one or more Type I emulsifiers by weight of the concentrated hair care composition, the one or more Type I emulsifiers having from about 5 to about 9 moles of ethoxylate, the one or more Type I emulsifiers having an HLB value of from about 10.3 to about 13;

ii) from about 0.5% to about 5% of one or more Type II emulsifiers by weight of the concentrated hair care composition, the one or more Type II emulsifiers having from about 2 to about 4.9 moles of ethoxylate, the one or more Type II emulsifiers having an HLB value of from about 8 to about 10.3; and

e) from about 60% to about 90% water, by weight of the concentrated hair care composition;

wherein the concentrated hair care composition has a silicone to high melting point fatty compound ratio of from about 80:20 to about 30:70, by weight of the silicone and by weight of the high melting point fatty compound;

wherein the concentrated hair care composition has a silicone to perfume ratio of from about 95:5 to about 50:50, by weight of the silicone and by weight of the perfume; and

wherein the concentrated hair care composition is rinse-off.